KR20190128147A - Luminescent displays, interlayers for laminated glass, laminated glass, and luminous display systems - Google Patents

Abstract

An object of the present invention is to provide a light emitting display having a simple structure which is thin and light, and which can display a three-dimensional image by irradiating light, an interlayer film for laminated glass including the light emitting display, a laminated glass, and a light emitting display system.
The present invention is a light emitting display having a light emitting layer containing a light emitting material that emits excitation light and emits light, and a reflective layer reflecting visible light.

Description

Luminescent displays, interlayers for laminated glass, laminated glass, and luminous display systems

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting display having a simple structure that is thin and light and capable of displaying a three-dimensional image by irradiating light, an interlayer film for laminated glass including the light emitting display, laminated glass, and a light emitting display system.

Laminated glass is widely used as front glass, side glass, rear glass of vehicles such as automobiles, and window glass such as aircraft, buildings, etc., because the glass fragments are less likely to scatter even when damaged by external impact. As laminated glass, laminated glass etc. which were integrated through the interlayer film for laminated glass containing a liquid plasticizer and a polyvinyl acetal resin, for example between at least one pair of glass are mentioned.

In recent years, the performance required for glass is also diversified, and the demand for information display and display development is particularly high. For example, there is a growing demand for displaying a gauge display such as speed information, which is vehicle driving data, as a head-up display (HUD) within the same field of view as a windshield for automobiles. On the other hand, in patent document 1, the applicant of this application disclosed the interlayer film for laminated glass which has a binder resin and the light emitting layer containing at least 1 sort (s) of light emitting material selected from the group which consists of a light emitting particle, a light emitting pigment, and a light emitting dye. . Light emitting materials such as light emitting particles, light emitting pigments, and light emitting dyes have a property of emitting light by irradiating light of a specific wavelength. By irradiating a light ray to the interlayer film for laminated glass containing such a light emitting material, the light-emitting particles to be emitted emit light, and an image with high contrast can be displayed.

On the other hand, a display that can be expressed in three dimensions is attracting attention as a field that is expected from many market trends associated with IT. For example, Patent Document 2 discloses a glazing unit that includes three glass plates and at least two plastic films alternately inserted between the glass plates, and a light emitter is introduced on at least one of the plastic film and the glass plate. It is. A three-dimensional image can be displayed by irradiating such glazing unit with the light which excites a light emitting body.

However, in order to display a three-dimensional image in the glazing unit described in Patent Literature 2, at least a glass plate / plastic film / glass plate / plastic film / glass plate requires a complicated structure requiring at least three glass plates. As a result, the glazing unit as a whole has to be thick and heavy, and there is a problem in that the use of available automobiles and buildings is limited.

Japanese Laid-Open Patent Publication No. 2014-24312 Japanese Patent Publication No. 2016-509563

SUMMARY OF THE INVENTION An object of the present invention is to provide a light emitting display having a simple structure which is thin and light, and which can display a three-dimensional image by irradiating light, an interlayer film for laminated glass including the light emitting display, a laminated glass, and a light emitting display system.

The present invention is a light emitting display having a light emitting layer containing a light emitting material that emits excitation light and emits light, and a reflective layer that reflects visible light.

The present invention is described in detail below.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination, the present inventors combined a light emitting layer containing the light emitting material which emits excitation light, and a reflecting layer which reflects visible light, and displays a three-dimensional image by irradiating light, although it is a very simple structure which is thin and light. What was possible was found and the present invention was completed.

In FIG. 1, the schematic diagram explaining the example of the light emitting display of this invention and the principle which displays a three-dimensional image by the light emitting display of this invention was shown.

In FIG. 1, the light emitting display 1 has a light emitting layer 11 and a reflective layer 12. Such a light emitting display 1 is irradiated from the light emitting layer 11 side with the light containing the light which excites visible light and the light emitting material contained in the light emitting layer 11 using the light source 2 (FIG. 1 (a)). ). As a result, the image 111 by emitting light from the luminescent material by the excitation light is displayed, and the image 121 by the visible light reflected by the reflective layer 12 is displayed. The image 111 and the image 121 are recognized as a three-dimensional image by the observer 3 on the light emitting layer 11 side in that a slight distance deviation occurs due to the thickness of each layer.

The light emitting layer contains a light emitting material that emits light upon receiving excitation light. Thereby, the light emitting layer itself can emit light by irradiating light, and an image can be displayed.

As said light emitting material, the lanthanoid complex which has a ligand containing a halogen atom is mentioned specifically from the point which can exhibit high luminescence, for example.

Among the lanthanoid complexes, lanthanoid complexes having a ligand containing a halogen atom emit light with high luminescence intensity by irradiation with light rays. Examples of the lanthanoid complex having a ligand containing a halogen atom include a lanthanoid complex having a single-seat ligand containing a halogen atom, a lanthanoid complex having a bidentate ligand containing a halogen atom, and a trident containing a halogen atom. A lanthanoid complex having a ligand, a lanthanoid complex having a tetradentate ligand containing a halogen atom, a lanthanoid complex having a 5 left ligand containing a halogen atom, a lanthanoid complex having a 6 left ligand containing a halogen atom, and the like. And lanthanoid complexes having polydentate ligands containing halogen atoms.

Especially, the lanthanoid complex which has a bidentate ligand containing a halogen atom, or the lanthanoid complex which has a tridentate ligand containing a halogen atom is a wavelength of 580-780 nm by irradiating light of the wavelength of 300-410 nm. Emits light with very high emission intensity. Since this light emission is very high intensity | strength, the light emitting display which has the light emitting layer containing this can emit light with comparatively high luminance even when the output irradiates the light with low intensity | strength.

Moreover, the lanthanoid complex which has a bidentate ligand containing the said halogen atom or the lanthanoid complex which has a tridentate ligand containing a halogen atom is also excellent in heat resistance. When a light-emitting display is used, for example as an interlayer film for laminated glass, for an automobile roof glass or a building window glass, it is often used in a high temperature environment by irradiating infrared rays of sunlight. Under such a high temperature environment, the light emitting material may deteriorate, and in particular, the light emitting material may deteriorate at an end portion of the laminated glass. By using a lanthanoid complex having a bidentate ligand containing the halogen atom or a lanthanoid complex having a tridentate ligand containing a halogen atom as the light emitting material, deterioration can be prevented even in a high temperature environment.

In the present specification, the lanthanoid includes lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. In view of obtaining higher emission intensity, the lanthanoid is preferably neodymium, europium or terbium, more preferably europium or terbium, still more preferably europium.

As a bidentate ligand containing the said halogen atom, the ligand which has a structure represented by following General formula (1), the ligand which has a structure represented by following General formula (2), etc. are mentioned, for example.

[Formula 1]

In the general formula (1), R ¹ and R ³ represents an organic group, R ¹ and R ³ of is at least one is an organic group containing a halogen atom, R ² has a carbon number of 1 or more straight-chain organic group of Indicates. It is preferable that said R <^1> and R <^3> is a hydrocarbon group, It is more preferable that it is a C1-C10 hydrocarbon group, It is still more preferable that it is a C1-C5 hydrocarbon group, It is especially preferable that it is a C1-C3 hydrocarbon group. Do. Some of the hydrogen atoms in the hydrocarbon group may be substituted with atoms and functional groups other than hydrogen atoms. As said C1-C3 hydrocarbon group, the methyl group, ethyl group, propyl group which a hydrogen atom is not substituted, the methyl group, ethyl group, propyl group etc. which some hydrogen atoms were substituted by the halogen atom are mentioned. Fluorine atom, chlorine atom, bromine atom, and iodine atom can be used as a halogen atom of the methyl group, the ethyl group, and the propyl group in which a part of the hydrogen atom is substituted by the halogen atom. As said C1-C3 hydrocarbon group, it is preferable that a part of a hydrogen atom is a methyl group, an ethyl group, and a propyl group substituted by a halogen atom, and it is more preferable that it is a trifluoromethyl group from the point which emits light with high luminescence intensity.

It is preferable that said R <^2> is a C1 or more alkylene group, It is more preferable that it is a C1-C5 alkylene group, It is most preferable that it is a methylene group of C1. Some of the hydrogen atoms may be substituted with atoms and functional groups other than a hydrogen atom in the said C1 or more alkylene group.

The lanthanoid complex having a ligand containing the halogen atom may have at least one ligand containing a halogen atom and may have a ligand containing no halogen atom. As a ligand which does not contain the said halogen atom, the ligand similar to the said General formula (1), the ligand which has a structure represented by following General formula (2)-(8) etc. are mentioned except not containing a halogen atom. . To a ligand having a structure represented by formula (2) to (8) is optionally substituted with any or all of the hydrogen _{atoms, -COOR, -SO 3, -NO 2} , -OH, alkyl, such as -NH _2.

[Formula 2]

In addition, in said Formula (2), two N may be anywhere in a bipyridine skeleton. For example, two N's at the 2,2 ', 3,3', 4,4 ', 2,3', 2,4 'and 3,4' positions of the bipyridine backbone. Can be mentioned. Especially, it is preferable that two N exists in a 2,2 'position.

[Formula 3]

In addition, in said Formula (3), two N may be anywhere in a bipyridine skeleton. Especially, it is preferable that two N exists in 1, 10 position.

[Formula 4]

In addition, in said Formula (4), two N may be anywhere in a bipyridine skeleton. Especially, it is preferable that two N exists in 1, 10 position.

[Formula 5]

In addition, in said Formula (5), three N may be anywhere in a terpyridine skeleton.

[Formula 6]

In the formula (6), the central R ⁴ represents a linear organic group having 1 or more carbon atoms.

[Formula 7]

In said Formula (7), two R <^5> represents a C1 or more linear organic group.

[Formula 8]

In the formula (8), n represents an integer of 1 or 2.

The lanthanoid complex having a bidentate ligand containing the halogen atom is, for example, tris (trifluoroacetylacetone) phenanthroline europium (Eu (TFA) ₃ phen), tris (trifluoroacetylacetone) diphenyl Phenanthroline europium (Eu (TFA) ₃ dpphen), tris (hexafluoroacetylacetone) diphenylphenanthroline europium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) europium, tris (trifluoro Acetylacetone) 2,2'-bipyridine europium, tris (hexafluoroacetylacetone) 2,2'-bipyridine europium, tris (5,5,6,6,7,7,7-heptafluoro-2 , 4-pentanedionate) 2,2'-bipyridine europium ([Eu (FPD) ₃ ] bpy), tris (trifluoroacetylacetone) 3,4,7,8-tetramethyl-1,10phenanthrol Lin europium ([Eu (TFA) ₃ ] tmphen), tris (5,5,6,6,7,7,7-heptafluoro-2,4-pentanedionate) phenanthroline europium ([Eu (FPD ) _3] phen), emitter pyridine trifluoroacetate As cetyl acetone europium, terpyridine hexafluoro acetylacetone, and the like europium.

The lanthanoid complex having a bidentate ligand containing the halogen atom may be, for example, tris (trifluoroacetylacetone) phenanthrolineterbium (Tb (TFA) ₃ phen), tris (trifluoroacetylacetone Diphenylphenanthroline terbium (Tb (TFA) ₃ dpphen), tris (hexafluoroacetylacetone) diphenylphenanthroline terbium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) terbium, tris ( Trifluoroacetylacetone) 2,2'-bipyridineterbium, tris (hexafluoroacetylacetone) 2,2'-bipyridineterbium, tris (5,5,6,6,7,7,7-heptafluoro Rho-2,4-pentanedionate) 2,2'-bipyridineterbium ([Tb (FPD) ₃ ] bpy), tris (trifluoroacetylacetone) 3,4,7,8-tetramethyl-1, 10-phenanthrolineterbium ([Tb (TFA) ₃ ] tmphen), tris (5,5,6,6,7,7,7-heptafluoro-2,4-pentanedionate) phenanthrolineterbium ([ _{Tb (FPD) 3] phen)} , terpyridine agent Fluoro and the like acetylacetone terbium, terpyridine hexafluoro acetylacetone terbium.

As the halogen atom of the lanthanoid complex having a ligand containing the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be used. Especially, a fluorine atom is preferable at the point which stabilizes the structure of a ligand.

Among the lanthanoid complexes having a bidentate ligand containing the halogen atom or the lanthanoid complexes having a tridentate ligand containing a halogen atom, in particular, the bidentate having a acetylacetone skeleton containing a halogen atom in terms of excellent initial luminescence Preference is given to lanthanoid complexes having ligands.

The lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing the halogen atom is, for example, Eu (TFA) ₃ phen, Eu (TFA) ₃ dpphen, Eu (HFA) ₃ phen, [Eu (FPD) ₃ ] bpy, [Eu (TFA) ₃ ] tmphen, [Eu (FPD) ₃ ] phen, and the like. The structure of the lanthanoid complex which has a bidentate ligand which has an acetylacetone frame | skeleton containing these halogen atoms is shown.

[Formula 9]

The lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing the halogen atom is, for example, Tb (TFA) ₃ phen, Tb (TFA) ₃ dpphen, Tb (HFA) ₃ phen, [Tb] (FPD) ₃ ] bpy, [Tb (TFA) ₃ ] tmphen, [Tb (FPD) ₃ ] phen and the like.

It is preferable that the lanthanoid complex which has a ligand containing the said halogen atom is particulate form. By being particulate, it becomes easier to undisperse the lanthanoid complex having a ligand containing the halogen atom in the binder resin.

When the lanthanoid complex having a ligand containing the halogen atom is in particulate form, the lower limit of the average particle diameter of the lanthanoid complex is preferably 0.01 µm, the upper limit is 10 µm, the lower limit is 0.03 µm, and the upper limit is 1 µm. to be.

As the light emitting material, a light emitting material having a terephthalic acid ester structure can also be used. The light emitting material having the terephthalic acid ester structure emits light by irradiating light rays.

As a light emitting material which has the said terephthalic acid ester structure, the compound which has a structure represented by the following general formula (10), and the compound which has a structure represented by following General formula (9) is mentioned, for example.

These may be used independently and may use 2 or more types.

[Formula 10]

In said general formula (9), R <^6> represents an organic group and x is 1, 2, 3 or 4.

In view of the higher transparency of the light emitting display, x is preferably 1 or 2, more preferably having a hydroxyl group at the 2 or 5 position of the benzene ring, and more preferably having a hydroxyl group at the 2 or 5 position of the benzene ring. More preferred.

It is preferable that the organic group of said R <^6> is a hydrocarbon group, It is more preferable that it is a C1-C10 hydrocarbon group, It is more preferable that it is a C1-C5 hydrocarbon group, It is especially preferable that it is a C1-C3 hydrocarbon group. .

When carbon number of the said hydrocarbon group is 10 or less, the light emitting material which has the said terephthalic acid ester structure can be easily disperse | distributed in binder resin.

It is preferable that the said hydrocarbon group is an alkyl group.

As a compound which has a structure represented by the said General formula (9), diethyl-2, 5- dihydroxy terephthalate, dimethyl-2, 5- dihydroxy terephthalate, etc. are mentioned, for example. Among them, the compound having a structure represented by the general formula (9) in that the image can be displayed at a higher brightness is diethyl-2,5-dihydroxyterephthalate (Aldrich, Ltd. "2,5 Diethyl dihydroxy terephthalate ").

In said general formula (10), R <^7> represents an organic group, R <^8> and R <^9> represents a hydrogen atom or an organic group, and y is 1, 2, 3 or 4.

It is preferable that the organic group of said R <^7> is a hydrocarbon group, It is more preferable that it is a C1-C10 hydrocarbon group, It is more preferable that it is a C1-C5 hydrocarbon group, It is especially preferable that it is a C1-C3 hydrocarbon group. .

If carbon number of the said hydrocarbon group is below the said upper limit, the light emitting material which has the said terephthalic acid ester structure can be easily disperse | distributed in binder resin.

It is preferable that the said hydrocarbon group is an alkyl group.

In said General Formula (10), NR ⁸ R ⁹ is an amino group. It is preferable that R <^8> and R <^9> are hydrogen atoms.

In the hydrogen atom of the benzene ring of the compound which has a structure represented by the said General formula (10), one hydrogen atom may be the said amino group, two hydrogen atoms may be the said amino group, three hydrogen atoms may be the said amino group, and four hydrogen may be sufficient as The amino group may be an atom.

As the compound having the structure represented by the general formula (10), diethyl-2,5-diaminoterephthalate (manufactured by Aldrich) is preferable because an image can be displayed at a higher luminance.

It is preferable that the said light emitting layer contains a thermoplastic resin as binder resin.

The said thermoplastic resin is not specifically limited, For example, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acryl copolymer resin, a polyurethane resin, the polyurethane resin containing a sulfur element, a polyvinyl alcohol resin, Vinyl chloride resin, polyethylene terephthalate resin, and the like. Especially, when using the light emitting display of this invention as an interlayer film for laminated glass, a polyvinyl acetal resin is preferable at the point which can exhibit the outstanding adhesiveness with respect to glass in combination with a plasticizer.

The polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal resins as needed.

The minimum with preferable acetalization degree of the said polyvinyl acetal resin is 40 mol%, a preferable upper limit is 85 mol%, a more preferable minimum is 60 mol%, and a more preferable upper limit is 75 mol%.

When using the light emitting display of this invention as an interlayer film for laminated glass, the said polyvinyl acetal resin has a preferable minimum of 15 mol%, and a preferable upper limit of 35 mol% of hydroxyl groups. If the amount of hydroxyl groups is 15 mol% or more, the molding of the interlayer film for laminated glass becomes easy. When the amount of hydroxyl groups is 35 mol% or less, the handling of the obtained interlayer film for laminated glass becomes easy.

In addition, the acetalization degree and the hydroxyl group amount can be measured based on JISK6728 "polyvinyl butyral test method", for example.

The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with aldehyde. The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used.

The minimum with preferable polymerization degree of the said polyvinyl alcohol is 500, and a preferable upper limit is 4000. When the polymerization degree of the said polyvinyl alcohol is 500 or more, the penetration resistance of the laminated glass manufactured using the light emitting display of this invention as an interlayer film for laminated glass becomes high. Molding becomes easy when the polymerization degree of the said polyvinyl alcohol is 4000 or less. The minimum with more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.

Although the said aldehyde is not specifically limited, In general, the C1-C10 aldehyde is used preferably. The aldehyde having 1 to 10 carbon atoms is not particularly limited, and for example, n-butylaldehyde, isobutylaldehyde, n-valeraldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonyl Aldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Especially, n-butylaldehyde, n-hexyl aldehyde, n-valeraldehyde is preferable, and n-butylaldehyde is more preferable. These aldehydes may be used independently and may use 2 or more types together.

As for content of the said luminescent material in the said light emitting layer, the preferable minimum with respect to 100 weight part of said thermoplastic resins is 0.001 weight part, and a preferable upper limit is 15 weight part. If content of the said luminescent material is 0.001 weight part or more, an image can be displayed by further higher luminance. When content of the said luminescent material is 15 weight part or less, transparency of a luminescent display becomes it still higher. The minimum with more preferable content of the said luminescent material is 0.01 weight part, a more preferable upper limit is 10 weight part, A more preferable minimum is 0.05 weight part, A more preferable upper limit is 8 weight part, Especially preferable minimum is 0.1 weight part, Especially preferable upper limit is 5 parts by weight, most preferably 1 part by weight.

It is preferable that the said light emitting layer contains a dispersing agent further. By containing a dispersing agent, aggregation of the said light emitting material can be suppressed and more uniform light emission is obtained.

The said dispersing agent is ester compounds, such as a compound which has sulfonic acid structures, such as a linear alkylbenzene sulfonate, a diester compound, a ricinolic acid alkyl ester, a phthalic ester, adipic acid ester, sebacic acid ester, and a phosphate ester, for example. Compound which has, compound which has ether structure, such as polyoxyethylene glycol, polyoxypropylene glycol, alkylphenyl-polyoxyethylene-ether, compound which has carboxylic acid structure, such as polycarboxylic acid, laurylamine, Compounds having an amine structure such as dimethyl lauryl amine, oleyl propylene diamine, secondary amine of polyoxyethylene, tertiary amine of polyoxyethylene, diamine of polyoxyethylene, and polyamine such as polyalkylene polyamine alkylene oxide Amide structures, such as a compound having a structure, and oleic acid diethanolamide, alkanol fatty acid amide A compound having, or polyvinyl pyrrolidone, dispersants such as polyester acid amide compound having a high molecular weight amide-type structure, such as an amine salt may be used. Moreover, you may use high molecular weight dispersing agents, such as polyoxyethylene alkyl ether phosphoric acid (salt), high molecular polycarboxylic acid, and condensation ricinolic acid ester. In addition, a high molecular weight dispersing agent is defined as the dispersing agent whose molecular weight is 10,000 or more.

When mix | blending the said dispersing agent, the minimum with preferable content of the said dispersing agent with respect to the said light emitting material in the said light emitting layer is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said dispersing agent is in this range, the said light emitting material can be disperse | distributed uniformly in binder resin. The minimum with more preferable content of the said dispersing agent is 3 weight part, a more preferable upper limit is 30 weight part, More preferably, a minimum is 5 weight part, and a more preferable upper limit is 25 weight part.

The light emitting layer may further contain an ultraviolet absorber. When the light emitting layer contains an ultraviolet absorber, the light resistance of the light emitting display is increased.

Since the image can be displayed at a higher luminance, the upper limit of the ultraviolet absorber in the light emitting layer is preferably 1 part by weight, more preferably 0.5 part by weight, more preferably 100 parts by weight of the thermoplastic resin. The preferred upper limit is 0.2 parts by weight, particularly preferably 0.1 part by weight.

The ultraviolet absorber has, for example, a compound having a malonic ester structure, a compound having an oxalate anhydride structure, a compound having a benzotriazole structure, a compound having a benzophenone structure, a compound having a triazine structure, and a benzoate structure. UV absorbers, such as a compound and a compound which has a hindered amine structure, are mentioned.

The light emitting layer may further contain a plasticizer.

The said plasticizer is not specifically limited, For example, organic ester plasticizers, such as monobasic organic acid ester and polybasic organic acid ester, phosphoric acid plasticizers, such as an organic phosphate plasticizer and an organic phosphite plasticizer, etc. are mentioned. It is preferable that the said plasticizer is a liquid plasticizer.

Although said monobasic organic acid ester is not specifically limited, For example, the glycol ester obtained by reaction of glycol and monobasic organic acid, etc. are mentioned. As said glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, etc. are mentioned, for example. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelagonic acid (n-nonyl acid), and decyl acid. Can be mentioned. Especially, triethylene glycol dicaproic acid ester, triethylene glycol di-2-ethyl butyric acid ester, triethylene glycol di-n-octylic acid ester, triethylene glycol di-2-ethylhexyl acid ester, etc. are preferable.

Although the said polybasic organic acid ester is not specifically limited, For example, ester compound of polybasic organic acids, such as adipic acid, sebacic acid, azelaic acid, and the alcohol which has a C4-C8 linear or branched structure is mentioned. . Especially, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester, etc. are preferable.

The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, triethylene glycol dicaprylate and triethylene glycol di-n-octanoate , Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adi Pate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyl Rate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene Glycol Dicapriate, Adi Acid dihexyl, dioctyl adipic acid, hexyl cyclohexyl adipic acid, diisononyl adipic acid, heptylnonyl adipic acid, dibutyl sebacate, oil-modified sebacic acid alkyd, mixture of phosphate ester and adipic acid ester, adipic C6-C8 adipic acid esters, such as mixed adipic acid ester manufactured from acid ester, C4-C9 alkyl alcohol, and C4-C9 cyclic alcohol, hexyl adipic acid, etc. are mentioned.

The said organic phosphate plasticizer is not specifically limited, For example, a tributoxy ethyl phosphate, an isodecyl phenyl phosphate, a triisopropyl phosphate, etc. are mentioned.

Among the above plasticizers, dihexyl adipate (DHA), triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol di-2-ethyl Group consisting of butyrate (3GH), tetraethyleneglycoldi-2-ethylbutylate (4GH), tetraethyleneglycoldi-n-heptanoate (4G7) and triethyleneglycoldi-n-heptanoate (3G7) It is preferable that it is at least 1 sort (s) chosen from.

Moreover, since it is hard to produce hydrolysis as said plasticizer, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH), tetraethylene glycol di-2- It is preferable to contain ethyl hexanoate (4GO) and dihexyl adipate (DHA). It is more preferable to contain tetraethylene glycol di-2-ethylhexanoate (4GO) and triethylene glycol di-2-ethylhexanoate (3GO). More preferably, triethylene glycol di-2-ethylhexanoate (3GO) is contained.

Although content of the said plasticizer in the said light emitting layer is not specifically limited, A preferable minimum with respect to 100 weight part of said thermoplastic resins is 30 weight part, and a preferable upper limit is 100 weight part. When content of the said plasticizer is 30 weight part or more, since the melt viscosity of a light emitting layer will become low, a light emitting display can be shape | molded easily. When content of the said plasticizer is 100 weight part or less, transparency of a light emitting display will become high. The minimum with more preferable content of the said plasticizer is 35 weight part, the more preferable upper limit is 80 weight part, The more preferable minimum is 45 weight part, More preferably, the upper limit is 70 weight part, Especially preferable minimum is 50 weight part, Especially preferable upper limit is 63 Parts by weight.

It is preferable that the said light emitting layer contains antioxidant from the point which can acquire the outstanding light resistance.

The said antioxidant is not specifically limited, The antioxidant which has a phenol structure, the antioxidant containing sulfur, the antioxidant containing phosphorus, etc. are mentioned.

The antioxidant which has the said phenol structure is antioxidant which has a phenol skeleton. As antioxidant which has the said phenol structure, For example, 2, 6- di-t- butyl- p-cresol (BHT), butylated hydroxyanisole (BHA), 2, 6- di-t- butyl- 4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 1,1,3- Tris- (2-methyl-hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4-hydroxyphenyl) propionate] methane, 1,3 , 3-tris- (2-methyl-4-hydroxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, bis (3,3'-t-butylphenol) butyric acid glycol ester, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) Propionate]. The said antioxidant may be used independently and may use 2 or more types together.

The said light emitting layer may contain an adhesive force regulator in order to adjust the adhesive force with respect to glass.

As said adhesive force regulator, at least 1 sort (s) chosen from the group which consists of an alkali metal salt, alkaline-earth metal salt, and magnesium salt is used preferably, for example. As said adhesive force regulator, salts, such as potassium, sodium, magnesium, are mentioned, for example.

As an acid which comprises the said salt, the organic acid of carboxylic acids, such as octylic acid, hexyl acid, 2-ethylbutyric acid, butyric acid, acetic acid, formic acid, or inorganic acids, such as hydrochloric acid and nitric acid, is mentioned, for example.

The said light emitting layer may contain additives, such as a light stabilizer, an antistatic agent, a blue pigment, a blue dye, a green pigment, and a green dye, as needed.

Although the thickness of the said light emitting layer is not specifically limited, A preferable minimum is 100 micrometers, and a preferable upper limit is 2000 micrometers. If the thickness of the light emitting layer is within this range, the image can be displayed with high luminance. The minimum with more preferable thickness of the said light emitting layer is 300 micrometers, a more preferable minimum is 350 micrometers, a more preferable upper limit is 1000 micrometers, and a still more preferable upper limit is 900 micrometers.

The light emitting display of this invention has a reflective layer. By combining the light emitting layer with the reflective layer, it is possible to display a three-dimensional image by irradiating with light even though the structure is very simple and thin.

The reflective layer is not particularly limited as long as it has a property of reflecting visible light, but the visible light reflectance is preferably 10% or more and 90% or less. If the visible light reflectance is within this range, three-dimensional images can be displayed more reliably. The minimum with said more preferable visible ray reflectance is 20%, and a more preferable upper limit is 80%.

In addition, in this specification, a visible light reflectance means the value measured according to JISR3106.

The reflective layer preferably has visible light transmittance of 30% or more and 95% or less. When the visible light transmittance of the reflective layer is within this range, it is possible to display a three-dimensional image and to exhibit excellent transparency and to be widely used in windshields, side glass, rear glass of vehicles such as automobiles, and window glass of aircraft, buildings, etc. Can be used. The minimum with more preferable visible light transmittance of the said reflection layer is 50%, and a more preferable upper limit is 90%.

In addition, in this specification, visible light transmittance means the value measured according to JISR3106.

Although the thickness of the said reflection layer is not specifically limited, A preferable minimum is 10 micrometers, and a preferable upper limit is 1000 micrometers. If the thickness of the said reflection layer is in this range, a three-dimensional image can be displayed more reliably. The minimum with more preferable thickness of the said reflection layer is 30 micrometers, a more preferable upper limit is 200 micrometers, and a more preferable upper limit is 100 micrometers.

As said reflection layer, commercial items, such as a combiner film (made by Defi, DF05702), can also be used, for example.

It is preferable that the light emitting display of this invention has a transparent layer further between a light emitting layer and a reflective layer. By having such a transparent layer, since the shift | offset | difference of the distance of the image on a light emitting layer and the image on a reflective layer becomes large by the thickness of the transparent layer, it is recognized by a viewer on the light emitting layer side as a more three-dimensional image. Moreover, by having a transparent layer, the intensity | strength of the light emitting display of this invention increases, and handling property improves.

It will not specifically limit, if it is transparent as said transparent layer, Organic plastic spans, such as a glass plate, a polyethylene terephthalate, a polycarbonate, and a polyacrylate, etc. are mentioned. Especially, a glass plate is preferable.

Although the thickness of the said transparent layer is not specifically limited, A preferable minimum is 300 micrometers, and a preferable upper limit is 1000 micrometers. If the thickness of the said transparent layer exists in this range, a three-dimensional image can be displayed. The minimum with more preferable thickness of the said transparent layer is 350 micrometers, and a more preferable upper limit is 900 micrometers.

The light emitting display of the present invention may have a space between the light emitting layer and the reflective layer. By providing a space between the light emitting layer and the reflective layer, the deviation of the distance between the image on the light emitting layer and the image on the reflective layer is increased, so that the viewer on the light emitting layer side is recognized as a three-dimensional image.

From the viewpoint of obtaining a more three-dimensional image, the width of the space between the light emitting layer and the reflective layer (distance between the light emitting layer and the reflective layer) is preferably 300 μm or more, more preferably 1 mm or more, and even more preferably 1 cm or more. Although the upper limit of the width of the space between the light emitting layer and the reflective layer is not particularly limited, it is preferably 5 m or less, more preferably 1 m or less, and even more preferably 10 cm or less from the viewpoint of minimizing the discomfort generated in stereoscopic vision. Do.

The light emitting display may have a transparent support plate on one side or both sides of the laminate of the light emitting layer and the reflective layer. By having a transparent support plate, the intensity | strength of the light emitting display of this invention increases, and handling property improves.

It will not specifically limit, if it is transparent as said transparent support plate, Organic plastic plates, such as a glass plate, a polyethylene terephthalate, a polycarbonate, and a polyacrylate, etc. are mentioned. Especially, a glass plate is preferable.

The light emitting display of the present invention has a simple structure which is thin and light, and can display a three-dimensional image by irradiating light.

The light source for irradiating light to the light emitting display of the present invention is a light source for irradiating the light of the excitation wavelength of the light emitting material (hereinafter referred to as "excitation light source"), and a light source for irradiating visible light reflected by the reflective layer (hereinafter referred to as , Also called "visible light source." Both the excitation light source and the visible light source may be mounted on one irradiation device, or a combination of one or more irradiation devices on which an excitation light source is mounted and one or more irradiation devices on which a visible light source is mounted may be used. And two or more irradiation apparatuses on which both visible light sources are mounted.

It is preferable that the said excitation light source is arrange | positioned at the said light emitting layer side of the light emitting display of this invention. The visible light source may be disposed on the light emitting layer side of the light emitting display of the present invention, or may be disposed on the reflective layer side.

The light ray irradiated from the excitation light source includes an excitation wavelength of the light emitting material and is selected according to the kind of the light emitting material. The excitation light source may be, for example, a spot light source (manufactured by Hamamatsu Photonics, "LC-8", etc.), a xenon flash lamp (manufactured by Hereus, "CW lamp", etc.), black light (manufactured by Yiwu Seongyoung Co., Ltd.). And "carry hand").

Although the output of the light beam irradiated from the said excitation light source is not specifically limited, It is preferable that it is 10 mW / cm <2> or more. By irradiating a light beam of 10 mW / cm 2 or more, an image with a higher luminance can be displayed. The minimum with more preferable output of the light to irradiate is 30 mW / cm <2>, a more preferable minimum is 50 mW / cm <2>, and an especially preferable minimum is 100 mW / cm <2>. Although the upper limit of the output of the light beam to irradiate is not specifically limited, 1000 mW / cm <2> or less is preferable from a viewpoint which does not unnecessarily enlarge an apparatus.

In addition, the output of the said light beam to irradiate is irradiated intensity measurement using the laser power meter (for example, "Oper Japan Corporation make," beam track power measurement sensor 3A-QUAD "etc.) arrange | positioned at the position 10 cm away from a light source. It can measure by.

The light ray irradiated from the said visible light source contains visible light, It does not specifically limit, A irradiation apparatus, such as a commercially available projector, can be used.

The light emitting display of this invention can be used widely as windshields, such as windshield, side glass, rear glass of vehicles, such as an automobile, and aircraft, buildings, etc. You may make the light emitting display of this invention the interlayer film for laminated glass, and manufacture laminated glass using this interlayer film for laminated glass.

The interlayer film for laminated glass including the light emitting display of the present invention is also one of the present invention.

Moreover, the laminated glass in which the interlayer film for laminated glass of this invention is laminated | stacked between a pair of glass plate is also one of this invention.

The interlayer film for laminated glass of the present invention may have a single layer structure composed of only the light emitting display of the present invention, or may have a multilayer structure in which a layer different from the light emitting display is laminated.

When the interlayer film for laminated glass has a multilayer structure, the light emitting display of the present invention may be disposed on the entire surface of the interlayer film for laminated glass, or may be disposed only on a portion thereof, and is in a plane direction perpendicular to the thickness direction of the interlayer film for laminated glass. It may be arrange | positioned at the whole surface of and may be arrange | positioned only to one part. When the light emitting display of this invention is arrange | positioned only in one part, it can be made to display an image only in a light emitting area by making a part into a light emitting area and the other part into a non-light emitting area.

In the case where the interlayer film for laminated glass has a multilayer structure, various functions may be imparted to the interlayer film for laminated glass obtained by adjusting the constituent components of the light emitting display and other layers of the present invention.

For example, in order to provide sound insulation performance to the said interlayer film for laminated glass, content of a plasticizer (henceforth content X) with respect to 100 weight part of thermoplastic resins in the light emitting display of this invention is called in another layer. It can be made more than content of a plasticizer (henceforth content Y.) with respect to 100 weight part of thermoplastic resins of this. In this case, the content X is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, more preferably 15 parts by weight or more than the content Y. Since the penetration resistance of the interlayer film for laminated glass becomes further higher, the difference between the content X and the content Y is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 35 parts by weight or less. In addition, the difference of the said content X and the said content Y is computed by (the difference of the said content X and the said content Y) = (the said content X-the said content Y).

The minimum with preferable content X is 45 weight part, a preferable upper limit is 80 weight part, A more preferable minimum is 50 weight part, A more preferable upper limit is 75 weight part, A more preferable minimum is 55 weight part, More preferably, an upper limit is 70 weight part. It is wealth. By making said content X more than the said minimum, high sound insulation can be exhibited. By making the said content X below the said preferable upper limit, generation | occurrence | production of the bleed out of a plasticizer can be suppressed and the fall of transparency and adhesiveness of the interlayer film for laminated glass can be prevented.

The minimum with preferable content Y is 20 weight part, a preferable upper limit is 45 weight part, A more preferable minimum is 30 weight part, A more preferable upper limit is 43 weight part, A more preferable minimum is 35 weight part, A more preferable upper limit is 41 weight part. It is wealth. By making the said content Y more than the said minimum, high penetration resistance can be exhibited. By making the said content Y below the said preferable upper limit, generation | occurrence | production of the bleed out of a plasticizer can be suppressed and the fall of transparency and adhesiveness of the interlayer film for laminated glass can be prevented.

Moreover, in order to provide sound insulation to the interlayer film for laminated glass of this invention, it is preferable that the thermoplastic resin in the light emitting display of this invention is polyvinyl acetal X. The said polyvinyl acetal X can be prepared by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. The minimum with preferable average degree of polymerization of the said polyvinyl alcohol is 200, and a preferable upper limit 5000 is preferable. By setting the average degree of polymerization of the polyvinyl alcohol to 200 or more, the penetration resistance of the obtained interlayer film for laminated glass can be improved, and by setting it to 5000 or less, the moldability of the light emitting display can be ensured. The minimum with more preferable average polymerization degree of the said polyvinyl alcohol is 500, and a more preferable upper limit is 4000. In addition, the average degree of polymerization of the said polyvinyl alcohol is calculated | required by the method based on JISK6726 "polyvinyl alcohol test method."

The minimum with preferable carbon number of the aldehyde for acetalizing the said polyvinyl alcohol is 4, and a preferable upper limit is 6. By making carbon number of an aldehyde four or more, a sufficient amount of plasticizer can be contained stably and the outstanding sound insulation performance can be exhibited. Moreover, the bleed out of a plasticizer can be prevented. By setting the aldehyde carbon number to 6 or less, the synthesis of polyvinyl acetal X can be facilitated, and productivity can be ensured. As said C4-C6 aldehyde, a linear aldehyde may be sufficient and a branched aldehyde may be sufficient, for example, n-butylaldehyde, n-valeraldehyde, etc. are mentioned.

The upper limit with preferable amount of hydroxyl groups of the said polyvinyl acetal X is 30 mol%. By making the amount of hydroxyl groups of the said polyvinyl acetal X into 30 mol% or less, the quantity of plasticizers required in order to exhibit sound insulation can be contained, and the bleed out of a plasticizer can be prevented. The upper limit of the amount of hydroxyl groups of the polyvinyl acetal X is more preferably 28 mol%, more preferably 26 mol%, particularly preferably the upper limit is 24 mol%, the lower limit is preferably 10 mol%, and the lower limit is more preferably 15 mol%. The minimum with preferable is 20 mol%.

The hydroxyl group amount of the said polyvinyl acetal X is the value which showed the mole fraction calculated | required by dividing the amount of the ethylene group which the hydroxyl group couple | bonds by the total amount of ethylene groups of a main chain, as a percentage (mol%). The amount of ethylene groups which the said hydroxyl group couple | bonds can be calculated | required by measuring the amount of the ethylene group which the hydroxyl group of the said polyvinyl acetal X couple | bonds, for example by the method based on JISK6728 "polyvinyl butyral test method."

The minimum with preferable acetal group amount of the said polyvinyl acetal X is 60 mol%, and a preferable upper limit is 85 mol%. By setting the amount of acetal groups of the polyvinyl acetal X to 60 mol% or more, the hydrophobicity of the light emitting display of the present invention can be increased, and the amount of plasticizer required to exhibit sound insulation can be contained, thereby bleeding out or whitening the plasticizer. Can be prevented. By making the amount of acetal groups of the said polyvinyl acetal X into 85 mol% or less, synthesis | combination of polyvinyl acetal X can be made easy and productivity can be ensured. 65 mol% is more preferable, and, as for the minimum of the acetal group amount of the said polyvinyl acetal X, 68 mol% or more is more preferable.

The amount of acetal groups can be determined by measuring the amount of ethylene groups to which the acetal group of polyvinyl acetal X is bonded by a method based on JIS K6728 "Polyvinyl butyral test method".

The minimum with preferable amount of acetyl groups of the said polyvinyl acetal X is 0.1 mol%, and a preferable upper limit is 30 mol%. By setting the amount of the acetyl groups of the polyvinyl acetal X to 0.1 mol% or more, the amount of plasticizer required to exhibit sound insulation can be contained, and bleed out can be prevented. Moreover, by making the amount of the acetyl groups of the said polyvinyl acetal X into 30 mol% or less, hydrophobicity of a light emitting layer can be made high and whitening can be prevented. The lower limit of the amount of the acetyl group of the polyvinyl acetal X is more preferably 1 mol%, further preferably 5 mol%, particularly preferably 8 mol%, more preferably 25 mol%, and even more preferably 20 mol%. .

The acetyl group amount is a percentage (mol%) obtained by dividing the amount of the ethylene group to which the acetal group is bonded and the amount of the ethylene group to which the hydroxyl group is bound from the total ethylene group of the main chain by dividing by the total ethylene group of the main chain. )

It is preferable that the said polyvinyl acetal X is polyvinyl acetal whose amount of said acetyl groups is 8 mol% or more, or polyvinyl acetal whose amount of the acetyl groups is less than 8 mol%, and the amount of acetal groups is 65 mol% or more. Thereby, the plasticizer of the quantity required for demonstrating sound insulation can be easily contained in the light emitting display of this invention. Moreover, it is more preferable that the said polyvinyl acetal X is polyvinyl acetal whose amount of said acetyl groups is 8 mol% or more, or polyvinyl acetal whose amount of the acetyl groups is less than 8 mol%, and 68 mol% or more of acetal groups is more preferable.

Moreover, in order to provide sound insulation to the interlayer film for laminated glass of this invention, it is preferable that the thermoplastic resin in the said other layer is polyvinyl acetal Y. It is preferable that polyvinyl acetal Y has larger amount of hydroxyl groups than polyvinyl acetal X.

The polyvinyl acetal Y can be prepared by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. Moreover, the preferable minimum of the average degree of polymerization of the said polyvinyl alcohol is 200, and a preferable upper limit is 5000. By setting the average degree of polymerization of the polyvinyl alcohol to 200 or more, the penetration resistance of the interlayer film for laminated glass can be improved, and by setting it to 5000 or less, the moldability of another layer can be ensured. The minimum with more preferable average polymerization degree of the said polyvinyl alcohol is 500, and a more preferable upper limit is 4000.

The minimum with preferable carbon number of the aldehyde for acetalizing the said polyvinyl alcohol is 3, and a preferable upper limit is 4. By making carbon number of an aldehyde three or more, the penetration resistance of the interlayer film for laminated glass becomes high. By making carbon number of an aldehyde 4 or less, productivity of polyvinyl acetal Y improves. As said C3-C4 aldehyde, a linear aldehyde may be sufficient and a branched aldehyde may be sufficient, for example, n-butylaldehyde etc. are mentioned.

The upper limit with preferable amount of hydroxyl groups of the said polyvinyl acetal Y is 33 mol%, and a preferable minimum is 28 mol%. By making the amount of hydroxyl groups of the said polyvinyl acetal Y into 33 mol% or less, whitening of the interlayer film for laminated glass can be prevented. By making the amount of hydroxyl groups of the said polyvinyl acetal Y into 28 mol% or more, the penetration resistance of the interlayer film for laminated glass becomes high.

The minimum with preferable acetal group amount of the said polyvinyl acetal Y is 60 mol%, and a preferable upper limit is 80 mol%. By making the acetal group amount 60 mol% or more, the amount of plasticizer required to exhibit sufficient penetration resistance can be contained. By making the amount of acetal groups into 80 mol% or less, the adhesive force of the said other layer and glass can be ensured. The minimum with more preferable acetal group amount of the said polyvinyl acetal Y is 65 mol%, and a more preferable upper limit is 69 mol%.

The upper limit with preferable amount of acetyl groups of the said polyvinyl acetal Y is 7 mol%. By making the amount of the acetyl groups of the said polyvinyl acetal Y into 7 mol% or less, hydrophobicity of another layer can be made high and whitening can be prevented. The upper limit with more preferable acetyl group quantity of the said polyvinyl acetal Y is 2 mol%, and a preferable minimum is 0.1 mol%.

In addition, the hydroxyl group amount, acetal group amount, and acetyl group amount of polyvinyl acetal Y can be measured by the method similar to polyvinyl acetal X.

For example, in order to provide heat shielding performance to the interlayer film for laminated glass, a heat ray absorber may be contained in any one layer, any two layers, or all layers of the light emitting display and the other layers of the present invention.

The heat ray absorbent is not particularly limited as long as it has the ability to shield infrared rays, but is not limited to tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, aluminum-doped zinc oxide (AZO) particles, and indium-doped zinc oxide (IZO). ), At least one member selected from the group consisting of tin-doped zinc oxide particles, silicon-doped zinc oxide particles, lanthanum hexaboride particles, and cerium hexaboride particles is preferable.

Although the thickness of the said interlayer film for laminated glass is not specifically limited, A preferable minimum is 50 micrometers, A preferable upper limit is 1700 micrometers, A more preferable minimum is 100 micrometers, A more preferable upper limit is 1000 micrometers, A more preferable upper limit is 900 micrometers. In addition, the minimum of the thickness of the interlayer film for laminated glass means the thickness of the minimum thickness part of the interlayer film for laminated glass, and the upper limit of the thickness of the interlayer film for laminated glass means the thickness of the maximum thickness portion of the interlayer film for laminated glass. do. In the case where the interlayer film for laminated glass has a multilayer structure, the thickness of the light emitting layer including the light emitting material is not particularly limited, but the lower limit is preferably 50 µm and the upper limit is preferably 1000 µm. When the thickness of the light emitting layer containing the light emitting material is within this range, light emission with sufficiently high contrast can be obtained when irradiating light rays of a specific wavelength. The minimum with more preferable thickness of the light emitting layer containing the said luminescent material is 80 micrometers, a more preferable upper limit is 500 micrometers, a further preferable minimum is 90 micrometers, and a more preferable upper limit is 300 micrometers.

The interlayer film for laminated glass of the present invention may have a wedge shape in cross-sectional shape. When the cross-sectional shape of the interlayer film for laminated glass is wedge-shaped, for example, when used as a head-up display, occurrence of a double phase can be prevented. It is preferable that the upper limit of the wedge-shaped wedge angle (theta) is 1 mrad from a viewpoint which makes a dual phase hard to produce. In addition, when the intermediate film for laminated glass with a wedge-shaped cross-sectional shape is manufactured by the method of extruding and shaping | molding a resin composition using an extruder, for example, the area | region inside a little from one end of a thin side (specifically, once When the distance between the other end and X is X, a shape having a minimum thickness may be formed in a region having a distance of 0X to 0.2X from one end of the thin side toward the inside. Moreover, the maximum thickness to a region slightly inward from one end of the thick side (specifically, an area of 0X to 0.2X from one end of the thick side toward the inside when the distance between one end and the other end is X) It may become a shape which has. In this specification, such a shape is also contained in a wedge shape.

When the cross-sectional shape of the interlayer film for laminated glass of the present invention is wedge-shaped, it may have a multilayer structure including the light emitting display of the present invention and another layer (hereinafter, may be referred to as a "shape auxiliary layer"). While the thickness of the light emitting display of the present invention is in a certain range, by laminating the shape auxiliary layer, the overall cross-sectional shape of the interlayer film for laminated glass can be adjusted to have a wedge shape having a constant wedge angle. Or by making at least one of the light emitting display and the said shape auxiliary layer of this invention into a wedge shape, it can be adjusted so that the cross-sectional shape of the whole interlayer film for laminated glass may become a wedge shape with a constant wedge angle. The shape auxiliary layer may be laminated only on one surface of the light emitting layer, or may be laminated on both surfaces. Moreover, you may laminate | stack a some shape auxiliary layer.

The manufacturing method of the said interlayer film for laminated glass is not specifically limited. For example, the plasticizer solution containing a plasticizer and a luminescent material, and a thermoplastic resin are fully mixed, and the resin composition for forming the interlayer film for laminated glass is manufactured. Next, the resin composition for forming the interlayer film for laminated glass can be extruded using an extruder to manufacture the interlayer film for laminated glass.

The said laminated glass is what laminated | stacked the said interlayer film for laminated glass between a pair of glass plates.

The transparent plate glass generally used can be used for the said glass plate. For example, inorganic glass, such as a float plate glass, a martens glass, a template glass, a reinforcement glass, a first input glass, a colored plate glass, a heat ray absorption glass, a heat ray reflection glass, green glass, is mentioned. Moreover, although the ultraviolet shielding glass in which the ultraviolet shielding coat layer was formed in the surface of glass can also be used, it is preferable to use as a glass plate opposite to the side which irradiates the light ray of a specific wavelength. Moreover, organic plastic spans, such as polyethylene terephthalate, polycarbonate, and polyacrylate, can also be used as said glass plate. As said glass plate, you may use two or more types of glass plates. For example, the laminated glass which laminated | stacked the said interlayer film for laminated glass between transparent float plate glass and colored glass plates, such as green glass, is mentioned. Moreover, you may use the glass plate from which 2 or more types of thickness differ as said glass plate.

A light emitting display system having a light emitting display of the present invention, a light source for irradiating light of an excitation wavelength of a light emitting material, and a light source for irradiating visible light reflected by a reflective layer is also one of the present inventions.

The light emitting display system which also has the interlayer film for laminated glass of this invention or the laminated glass of this invention, the light source which irradiates the light of the excitation wavelength of a luminescent material, and the light source which irradiates the visible light which a reflection layer reflects is also one of this invention. .

According to the present invention, it is possible to provide a light emitting display having a simple structure which is thin and light and capable of displaying three-dimensional images by irradiating light, an interlayer film for laminated glass including the light emitting display, laminated glass, and a light emitting display system.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the example of the light emitting display of this invention, and the principle which displays a three-dimensional image by the light emitting display of this invention.

Although an Example is given to the following and the aspect of this invention is demonstrated in more detail, this invention is not limited only to these Examples.

(Example 1)

(1) Preparation of polyvinyl butyral

In a 2 m 3 reactor equipped with a stirrer, 1700 kg of 7.5 mass% aqueous solution of PVA (polymerization degree 1700, saponification degree 99 mol%) and 74.6 kg n-butylaldehyde, 2,6-di-t-butyl-4-methylphenol 0.13 kg was injected and the whole was cooled to 14 ° C. 99.44 L of nitric acid of 30 mass% of concentration was added to this, and butyralization of PVA was started. 10 minutes after the completion | finish of addition, temperature rising was started, it heated up to 65 degreeC over 90 minutes, and reaction was performed for 120 minutes. Then, the solid content which cooled to room temperature and precipitated was filtered, and it wash | cleaned 10 times with 10 times of ion-exchange water by mass with respect to solid content. Thereafter, neutralization is sufficiently carried out using a 0.3 mass% sodium hydrogen carbonate aqueous solution, and further washed with 10 times the amount of ion-exchanged water by mass with respect to solids, dehydrated, and dried, followed by polyvinyl butyral resin. (PVB) was obtained.

(2) manufacture of light emitting displays and laminated glass

Diethyl-2,5-dihydroxyterephthalate ("2,5-dihydroxyterephthalate diethyl" manufactured by Aldrich) 0.54 to 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) A weight part was added and the luminescent plasticizer solution was prepared. The resin composition was prepared by fully kneading the obtained plasticizer solution and 100 weight part of obtained polyvinyl butyral with a mixing roll.

The obtained resin composition was extruded using the extruder and the light emitting layer of 350 micrometers in thickness was obtained.

A resin composition was prepared by fully kneading 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) and 100 parts by weight of the obtained polyvinyl butyral with a mixing roll.

The obtained resin composition was extruded using the extruder and the resin film layer of 350 micrometers in thickness was obtained.

A combiner film (DF05702, manufactured by Defi Co., Ltd.) was prepared as a reflective layer, which was sandwiched with a light emitting layer and a resin film to obtain a laminated film composed of a light emitting layer / reflective layer / resin film layer.

The obtained laminated | multilayer film was laminated | stacked between a pair of clear glass (thickness 2.5mm) of length 5cm x width 5cm as an interlayer film for laminated glass, and the laminated body was obtained. The obtained laminated body was vacuum-pressed and crimped | bonded, holding | maintaining at 90 degreeC for 30 minutes with a vacuum laminator. After crimping | bonding was crimped | bonded for 20 minutes using the autoclave on 140 degreeC and 14 MPa conditions, and the laminated glass was obtained.

(Example 2)

12.5 mmol of europium acetate (Eu (CH ₃ COO) ₃ ) was dissolved in 50 mL of distilled water, 33.6 mmol of trifluoroacetylacetone (TFA, CH ₃ COCH ₂ COCF ₃ ) was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and then recrystallized with methanol and distilled water to obtain Eu (TFA) ₃ (H ₂ O) ₂ . 5.77 g of the obtained complex Eu (TFA) ₃ (H ₂ O) ₂ and 2.5 g of 1,10-phenanthroline (phen) were dissolved in 100 mL of methanol, and heated to reflux for 12 hours. After 12 hours, methanol was removed by distillation under reduced pressure to obtain a white product. After wash | cleaning this powder with toluene and removing unreacted raw material by suction filtration, toluene was distilled off under reduced pressure and powder was obtained. Eu (TFA) ₃ phen was obtained by recrystallization with a mixed solvent of toluene and hexane.

About 40 parts by weight of 3GO, diethyl-2,5-dihydroxy terephthalate (Aldrich Co., Ltd., "2,5-dihydroxy-terephthalic acid diethyl"), 0.54 parts by weight of Eu (TFA) thus obtained, in place of ₃ phen A light emitting display and a laminated glass were produced in the same manner as in Example 1 except that 0.4 parts by weight was used.

(Example 3)

12.5 mmol of terbium acetate (Tb (CH ₃ COO) ₃ ) was dissolved in 50 mL of distilled water, 33.6 mmol of trifluoroacetylacetone (TFA, CH ₃ COCH ₂ COCF ₃ ) was added, and the mixture was stirred at room temperature for 3 hours. The precipitated solid was filtered, washed with water, and then recrystallized with methanol and distilled water to obtain Tb (TFA) ₃ (H ₂ O) ₂ . 5.77 g of the obtained complex Tb (TFA) ₃ (H ₂ O) ₂ and 2.5 g of 1,10-phenanthroline (phen) were dissolved in 100 mL of methanol, and heated to reflux for 12 hours. After 12 hours, methanol was removed by distillation under reduced pressure to obtain a white product. After wash | cleaning this powder with toluene and removing unreacted raw material by suction filtration, toluene was distilled off under reduced pressure and powder was obtained. Tb (TFA) ₃ phen was obtained by recrystallization with a mixed solvent of toluene and hexane.

About 40 parts by weight of 3GO, diethyl-2,5-dihydroxy terephthalate (Aldrich Co., Ltd., "2,5-dihydroxy-terephthalic acid diethyl"), 0.54 parts by weight of the Tb (TFA) thus obtained, in place of ₃ phen A light emitting display and a laminated glass were produced in the same manner as in Example 1 except that 0.4 parts by weight was used.

(Comparative Example 1)

A light emitting display and a laminated glass were produced in the same manner as in Example 1 except that no reflective layer was used.

(Comparative Example 2)

Using the resin film layer instead of the light emitting layer, the laminated film which consists of a resin film layer / a reflection layer / resin film layer was obtained, and it carried out similarly to Example 1 except having used this, and produced the light emitting display and laminated glass.

(evaluation)

About the laminated glass obtained by the Example and the comparative example, it evaluated by the following method.

The results are shown in Table 1.

(Evaluation of three-dimensional image display)

The laminated glass of 5 cm x 5 cm in length obtained by the Example and the comparative example was arrange | positioned under a dark room, and the light source was arrange | positioned in the position 10 cm apart in the perpendicular direction with respect to the surface of the laminated glass. Next, the observer was arrange | positioned at the side which the shortest distance from the surface of the laminated glass becomes 35 cm at the angle of 20 degrees from the surface of the laminated glass which irradiated light, and irradiated the light. And light was irradiated with laminated glass from the irradiation apparatus, the image displayed on the laminated glass was observed, and the following references | standards evaluated. However, in Comparative Example 2, the image itself was not displayed.

(Circle): A three-dimensional image was displayed.

X: The three-dimensional image was not displayed.

Industrial availability

According to the present invention, it is possible to provide a light emitting display having a simple structure which is thin and light and capable of displaying three-dimensional images by irradiating light, an interlayer film for laminated glass including the light emitting display, laminated glass, and a light emitting display system.

1: luminous display
11: light emitting layer
111: image by emitting light from a light emitting material by excitation light
12: reflective layer
121: Image by visible light reflected by the reflection layer 12
2: light source
3: observer

Claims (8)

A light emitting display comprising a light emitting layer containing a light emitting material that emits excitation light and emits light, and a reflective layer that reflects visible light. The method of claim 1,
The reflective layer has a visible light reflectance of 10% or more and 90% or less. The method according to claim 1 or 2,
The reflective layer has a visible light transmittance of 30% or more and 95% or less. The method according to claim 1, 2 or 3,
A light emitting display further comprising a transparent layer between the light emitting layer and the reflective layer. An interlayer film for laminated glass, comprising the light emitting display according to claim 1, 2, 3 or 4. The laminated film for laminated glass of Claim 5 is laminated | stacked between a pair of glass plate, The laminated glass characterized by the above-mentioned. The light-emitting display of Claim 1, 2, 3, or 4, the light source which irradiates the light of the excitation wavelength of a luminescent material, and the light source which irradiates the visible light which a reflection layer reflects, It is characterized by the above-mentioned. Luminous display system. The interlayer film for laminated glass of Claim 5 or the laminated glass of Claim 6, the light source which irradiates the light ray of the excitation wavelength of a luminescent material, and the light source which irradiates the visible light which a reflection layer reflects, The light-emitting display characterized by the above-mentioned. system.

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